Oral care compositions having improved consumer aesthetics and taste

ABSTRACT

The present invention relates to peroxide containing oral care compositions containing a flavor system that effectively masks the undesirable taste and sensations due to peroxide. The flavor system comprises menthol, at least one other secondary coolant and selected flavor chemicals that together provide a stable flavor profile and a high impact refreshing taste and sensation. The secondary coolant is selected from carboxamides, ketals, diols, menthyl esters and mixtures thereof.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.60/786,942, filed Mar. 29, 2006.

TECHNICAL FIELD

The present invention relates to oral care compositions containing aflavor system that effectively masks the undesirable taste andsensations due to certain ingredients. In particular, the ingredientwith undesirable aesthetics is peroxide, which is included in dentifriceand mouthrinse compositions for its whitening and antimicrobialbenefits. The taste and mouthfeel of oral care products are particularlyimportant for consumer acceptability and compliance since use of theseproducts necessarily involve fairly long residence time in the mouth forefficacy.

BACKGROUND OF THE INVENTION

Oral care products such as dentifrice and mouthrinse are routinely usedby consumers as part of their oral care hygiene regimens. It is wellknown that oral care products can provide both therapeutic and cosmetichygiene benefits to consumers. Therapeutic benefits include cariesprevention which is typically delivered through the use of variousfluoride salts; gingivitis prevention by the use of an antimicrobialagent such as triclosan, stannous fluoride, or essential oils; orhypersensitivity control through the use of ingredients such asstrontium chloride or potassium nitrate. Cosmetic benefits provided byoral care products include the control of plaque and calculus formation,removal and prevention of tooth stain, tooth whitening, breathfreshening, and overall improvements in mouth feel impression which canbe broadly characterized as mouth feel aesthetics. Calculus and plaquealong with behavioral and environmental factors lead to formation ofdental stains, significantly affecting the aesthetic appearance ofteeth. Behavioral and environmental factors that contribute to teethstaining propensity include regular use of coffee, tea, cola or tobaccoproducts, and also the use of certain oral products containingingredients that promote staining, such as cationic antimicrobials andmetal salts.

Thus daily oral care at home requires products with multiple ingredientsworking by different mechanisms to provide the complete range oftherapeutic and aesthetic benefits, including anticaries, antimicrobial,antigingivitis, antiplaque and anticalculus as well as antiodor, mouthrefreshment, stain removal, stain control and tooth whitening. In orderfor oral care products for daily use such as dentifrice and rinses toprovide complete oral care it is necessary to combine actives andadditives, many of which have the disadvantage of causing negativeaesthetics during use, in particular unpleasant taste and sensations andstain promotion. The unpleasant taste and mouth sensations have beendescribed as having one or more of bitter, metallic, astringent, salty,numbing, stinging, burning, prickling, and evens irritating aspects.Typical ingredients for oral care use that are associated with theseaesthetic negatives include antimicrobial agents such as cetylpyridinium chloride, chlorhexidine, stannous and zinc salts; toothbleaching agents such as peroxides; antitartar agents such aspyrophosphate, tripolyphosphate and hexametaphosphate; and excipientssuch as baking soda and surfactants. To mitigate the aesthetic negativesfrom these ingredients, oral care products are typically formulated withflavoring agents and sweeteners to taste as good as possible and beconsumer. acceptable.

Although there have been many advances in oral care product formulationsin recent years, there is still a need for improved products,particularly peroxide containing products with improved aesthetics andtaste. Flavoring peroxide containing products' presents significantchallenges for the formulator because the unpleasant taste andsensations derived from peroxide are difficult to mask and because manytraditional flavor components are not sufficiently stable in thepresence of peroxide. The present invention provides an improved flavorsystem comprising selected traditional flavor components combined with amixture of menthol with at least one other coolant. The improved flavorsystem effectively masks the unpleasant taste and sensations derivedfrom peroxide and provide a refreshing taste and sensation preferred byconsumers.

SUMMARY OF THE INVENTION

The present invention is directed to oral care compositions comprising

(a) a, peroxide source,

(b) a flavor composition comprising menthol, a secondary coolant and oneor a mixture of selected flavor components that maintain a stableprofile in the presence of peroxide, and

(c) an orally-acceptable carrier comprising excipients and diluents,which are capable of being commingled with the peroxide withoutsubstantially interacting with the peroxide in a manner which wouldsubstantially reduce the stability of the composition. The compositionshave a stable, well-rounded flavor profile and are pleasant tasting andrefreshing, thereby encouraging user compliance and frequent use.

These and other features, aspects, and advantages of the presentinvention will become evident to those skilled in the art from thedetailed description which follows.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims particularly pointing outand distinctly claiming the invention, it is believed that the presentinvention will be better understood from the following description.

All percentages and ratios used hereinafter are by weight of totalcomposition, unless otherwise indicated. All percentages, ratios, andlevels of ingredients referred to herein are based on the actual amountof the ingredient, and do not include solvents, fillers, or othermaterials with which the ingredient may be combined as a commerciallyavailable product, unless otherwise indicated.

All measurements referred to herein are made at 25° C. unless otherwisespecified.

Herein, “comprising” means that other steps and other components whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of.”

As used herein, the word “include,” and its variants, are intended to benon-limiting, such that recitation of items in a list is not to theexclusion of other like items that may also be useful in the materials,compositions, devices, and methods of this invention.

As used herein, the words “preferred”, “preferably” and variants referto embodiments of the invention that afford certain benefits, undercertain circumstances. However, other embodiments may also be preferred,under the same or other circumstances. Furthermore, the recitation ofone or more preferred embodiments does not imply that other embodimentsare not useful, and is not intended to exclude other embodiments fromthe scope of the invention.

By “oral care composition” is meant a product, which in the ordinarycourse of usage, is not intentionally swallowed for purposes of systemicadministration of particular therapeutic agents, but is rather retainedin the oral cavity for a time sufficient to contact substantially all ofthe dental surfaces and/or oral tissues for purposes of oral activity.The oral care composition may be in various forms including toothpaste,dentifrice, tooth gel, subgingival gel, mouthrinse, mousse, foam,denture product, mouthspray, lozenge, chewable tablet or chewing gum.The oral care composition may also be incorporated onto strips or filmsfor direct application or attachment to oral surfaces.

The term “dentifrice”, as used herein, means paste, gel, or liquidformulations unless otherwise specified. The dentifrice composition maybe a single phase composition or may be a combination of two or moreseparate dentifrice compositions. The dentifrice composition may be inany desired form, such as deep striped, surface striped, multilayered,having the gel surrounding the paste, or any combination thereof. Eachdentifrice composition in a dentifrice comprising two or more separatedentifrice compositions may be contained in a physically separatedcompartment of a dispenser and dispensed side-by-side.

The term “dispenser”, as used herein, means any pump, tube, or containersuitable for dispensing compositions such as dentifrices.

The term “teeth”, as used herein, refers to natural teeth as well asartificial teeth or dental prosthesis.

The term “orally acceptable carrier or excipients” includes materialssafe and effective materials and conventional additives used in oralcare compositions including but not limited to fluoride ion sources,anti-calculus or anti-tartar agents, buffers, abrasives such as silica,alkali metal bicarbonate salts, thickening materials, humectants, water,surfactants, titanium dioxide, flavor system, sweetening agents,xylitol, coloring agents, and mixtures thereof.

Active and other ingredients useful herein may be categorized ordescribed herein by their cosmetic and/or therapeutic benefit or theirpostulated mode of action or function. However, it is to be understoodthat the active and other ingredients useful herein can, in someinstances, provide more than one cosmetic and/or therapeutic benefit orfunction or operate via more than one mode of action. Therefore,classifications herein are made for the sake of convenience and are notintended to limit an ingredient to the particularly stated applicationor applications listed.

Herein, the terms “tartar” and “calculus” are used interchangeably andrefer to mineralized dental plaque biofilms.

The essential and optional components of the present compositions aredescribed in the following paragraphs.

Peroxide Source

The present compositions contain a peroxide source as a first essentialingredient for its many benefits to the oral, cavity. It has long beenrecognized that hydrogen peroxide and other peroxygen-containing agentsare effective in curative and/or prophylactic treatments with respect tocaries, dental plaque, gingivitis, periodontitis, mouth odor, toothstains, recurrent aphthous ulcers, denture irritations, orthodonticappliance lesions, postextraction and postperiodontal surgery, traumaticoral lesions and mucosal infections, herpetic stomatitis and the like.Peroxide-containing agents in the oral cavity exert a chemomechanicalaction generating thousands of tiny oxygen bubbles produced byinteraction with tissue and salivary enzymes. The swishing action of amouthrinse enhances this inherent chemomechanical action. Such actionhas been recommended for delivery of other agents into infected gingivalcrevices. Peroxide mouthrinses prevent colonization and multiplicationof anaerobic bacteria known to be associated with periodontal disease.However, compositions containing hydrogen peroxide or other peroxidereleasing compounds generally provide disagreeable taste and mouthsensations. These sensations have been described as stinging, pricklingand irritating, similar to that experienced when the tongue comes intocontact with sharp flavors or highly carbonated liquids such as clubsoda. In addition peroxides interact with other common excipientstherein and tend to be unstable in storage, continuously losing thecapacity to release active or nascent oxygen over relatively shortperiods of time, and tend to diminish or destroy the desired function ofsuch excipients. Among such excipients are flavors, sensory materialsand coloring agents added to enhance the acceptability of the oral careproduct to those in need of an oral peroxidizing or bleaching treatment.

Peroxide sources include peroxide compounds, perborates, percarbonates,peroxyacids, persulfates, and combinations thereof. Suitable peroxidecompounds include hydrogen peroxide, urea peroxide, calcium peroxide,sodium peroxide, zinc peroxide and mixtures thereof. A preferredpercarbonate is sodium percarbonate. Preferred persulfates are oxones.Preferred peroxide sources for use in dentifrice formulations includecalcium peroxide and urea peroxide. Hydrogen peroxide and urea peroxideare preferred for use in mouthrinse formulations. The following amountsrepresent the amount of peroxide raw material, although the peroxidesource may contain ingredients other than the peroxide raw material. Thepresent composition may contain from about 0.01% to about 30%,preferably from about 0.1% to about 10%, and more preferably from about0.5% to about 5% of a peroxide source, by weight of the composition.

Flavor System

A flavor system that effectively masks the unpleasant taste andsensations due to the peroxide component is the second essentialcomponent of the composition. Pleasant tasting compositions improve usercompliance to prescribed or recommended use of peroxide containingproducts. The present flavor system comprises menthol as a first coolantin combination with at least one secondary cooling agent along withselected traditional flavor components that have been found to berelatively stable in the presence of peroxide. By “stable” herein ismeant that the flavor character or profile does not significantly changeor is consistent during the life of the product. Thus, the flavorcomponents may undergo some degradation during the life of the product;however this does not result in a significant change in the flavorcharacter or profile or its acceptability. The combination of theselected flavoring agents with the coolants provides a high-impactrefreshing sensation with a well-rounded flavor profile that effectivelymasks the unpleasant peroxide taste and sensations.

The oral care composition will comprise from about 0.04%. to 1.5% totalcoolants (menthol+secondary coolant) with at least about 0.015% mentholby weight. Typically, the level of menthol in the final compositionranges from about 0.015% to about 1.0% and the level of secondarycoolant(s) ranges from about 0.01% to about 0.5%. Preferably, the levelof total coolants ranges from about 0.03% to about 0.6%.

Suitable secondary cooling agents or coolants to be used with mentholinclude a wide variety of materials such as carboxamides, ketals, diols,menthyl esters and mixtures thereof. Examples of secondary coolants inthe present compositions are the paramenthan carboxamide agents such asN-ethyl-p-menthan-3-carboxamide, known commercially as “WS-3”,N,2,3-trimethyl-2-isopropylbutanamide, known as, “WS-23”, and others inthe series such as WS-5, WS-11, WS-14 and WS-30. Additional suitablecoolants include 3-1-menthoxypropane-1,2-diol known as TK-10manufactured by Takasago; menthone glycerol acetal known as MGA; menthylesthers such as menthyl acetate, menthyl acetoacetate, menthyl lactateknown as Frescolat® supplied by Haarmann and Reimer, and monomenthylsuccinate under the tradename Physcool from V. Manė. The terms mentholand menthyl as used herein include dextro- and levorotatory isomers ofthese compounds and racemic mixtures thereof. TK-10 is described in U.S.Pat. No. 4,459,425, Amano et al., issued Jul. 10, 1984. WS-3 and otheragents are described in U.S. Pat. No. 4,136,163, Watson, et al., issuedJan. 23, 1979.

Traditional flavor components that have been found to be relativelystable in the presence of peroxide include methyl salicylate, ethylsalicylate, methyl cinnamate, ethyl cinnamate, butyl cinnamate, ethylbutyrate, ethyl acetate, methyl anthranilate, iso-amyl acetate,iso-armyl butyrate, allyl caproate, eugenol, eucalyptol, thymol,cinnamic alcohol, cinnamic aldehyde, octanol, octanal, decanol, decanal,phenylethyl alcohol, benzyl alcohol, benzaldehyde, alpha-terpineol,linalool, limonene, citral, vanillin, ethyl vanillin, propenyl guaethol,maltol, ethyl maltol, heliotropin, anethole, dihydroanethole, carvone,oxanone, menthone, β-damascenone, ionone, gamma decalactone, gammanonalactone, gamma undecalactone, 4-hydroxy-2,5-dimethyl-3(2H)-furanoneand mixtures thereof. Generally suitable flavoring agents are thosecontaining structural features and functional groups that are less proneto oxidation by peroxide. These include derivatives of flavor chemicalsthat are saturated or contain stable aromatic rings or ester groups.Also suitable are flavor chemicals that may undergo some oxidation ordegradation without resulting in a significant change in the flavorcharacter or profile. It is preferred that the flavor chemicalsincluding menthol are provided as single or purified chemicals ratherthan supplied in the composition by addition of natural oils or extractssuch as peppermint, spearmint or wintergreen oils as these sources maycontain other components that are relatively unstable and may degrade inthe presence of peroxide. Such degradation may significantly alter thedesired flavor profile and result in a less acceptable product from anorganoleptic standpoint. In a blind use test, consumers preferred aperoxide rinse (Example IC below) flavored with an artificial mintcontaining only purified chemicals than the same formula flavored with asimilar mint flavor containing some natural oils, although both flavorswere acceptable. Thus even if flavor chemicals undergo degradation andproduce off-notes, the present coolant combination appears toeffectively mask such off-notes. Flavoring agents are generally used inthe compositions at levels of from about 0.001% to about 5%, by weightof the composition.

The flavor system will typically include a sweetening agent. Suitablesweeteners include those well known in the art, including both naturaland artificial sweeteners. Some suitable water-soluble sweetenersinclude monosaccharides, disaccharides and polysaccharides such asxylose, ribose, glucose (dextrose), mannose, galactose, fructose(levulose), sucrose (sugar), maltose, invert sugar (a mixture offructose and glucose derived from sucrose), partially hydrolyzed starch,corn syrup solids, dihydrochalcones, monellin, steviosides, andglycyrrhizin. Suitable water-soluble artificial sweeteners includesoluble saccharin salts, i.e., sodium or calcium saccharin salts,cyclamate salts, the sodium, ammonium or calcium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide, the potassiumsalt of 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide(acesulfame-K), the free acid form of saccharin, and the like. Othersuitable sweeteners include Dipeptide based sweeteners, such asL-aspartic acid derived sweeteners, such as L-aspartyl-L-phenylalaninemethyl ester (aspartame) and materials described in U.S. Pat. No.3,492,131,L-alpha-aspartyl-N-(2,2,4,4-tetramethyl-3-thietanyl)-D-alaninamidehydrate, methyl esters of L-aspartyl-L-phenylglycerin andL-aspartyl-L-2,5,dihydrophenyl-glycine,L-aspartyl-2,5-dihydro-L-phenylalanine,L-aspartyl-L-(1-cyclohexyen)-alanine, and the like. Water-solublesweeteners derived from naturally occurring water-soluble sweeteners,such as a chlorinated derivative of ordinary sugar (sucrose), known, forexample, under the product description of sucralose as well as proteinbased sweeteners such as thaumatoccous danielli (Thaumatin I and II) canbe used. A composition preferably contains from about 0.1% to about 10%of sweetener, preferably from about 0.1% to about 1%, by weight of thecomposition.

In addition the flavor system may include salivating agents, warmingagents, and numbing agents. These agents are present in the compositionsat a level of from about 0.001% to about 10%, preferably from about 0.1%to about 1%, by weight of the composition. Suitable salivating agentsinclude Jambus manufactured by Takasago. Examples of warming agents arecapsicum and nicotinate esters, such as benzyl nicotinate. Suitablenumbing agents include benzocaine, lidocaine, clove bud oil, andethanol.

In addition to the components described above, the present compositionsmay comprise additional optional components collectively referred to asorally acceptable carrier materials, which are described in thefollowing paragraphs:

Orally Acceptable Carrier Materials

The orally acceptable carrier comprises one or more compatible solid orliquid excipients or diluents which are suitable for topical oraladministration. By “compatible,” as used herein, is meant that thecomponents of the composition are capable of being commingled withoutinteraction in a manner which would substantially reduce thecomposition's stability and/or efficacy.

The carriers or excipients of the present invention can include theusual and conventional components of dentifrices, non-abrasive gels,subgingival gels, mouthwashes or rinses, mouth sprays, chewing gums,lozenges and breath mints as more fully described hereinafter.

The choice of a carrier to be used is basically determined by the waythe composition is to be introduced into the oral cavity. Carriermaterials for toothpaste, tooth gel or the like include abrasivematerials, sudsing agents, binders, humectants, flavoring and sweeteningagents, etc. as disclosed in e.g., U.S. Pat. No. 3,988,433, to Benedict.Carrier materials for biphasic dentifrice formulations are disclosed inU.S. Pat. No. 5,213,790, issued May 23, 1993, U.S. Pat. No. 5,145,666,issued Sep. 8, 1992, and U.S. Pat. No. 5,281,410 issued Jan. 25, 1994all to Lukacovic et al. and in U.S. Pat. Nos. 4,849,213 and 4,528,180 toSchaeffer. Mouthwash, rinse or mouth spray carrier materials typicallyinclude water, flavoring and sweetening agents, etc., as disclosed in,e.g., U.S. Pat. No. 3,988,433 to Benedict. Lozenge carrier materialstypically include a candy base; chewing gum carrier materials include agum base, flavoring and sweetening agents, as in, e.g., U.S. Pat. No.4,083,955, to Grabenstetter et al. Sachet carrier materials typicallyinclude a sachet bag, flavoring and sweetening agents. For subgingivalgels used for delivery of actives into the periodontal pockets or aroundthe periodontal pockets, a “subgingival gel carrier” is chosen asdisclosed in, e.g. U.S. Pat. Nos. 5,198,220 and 5,242,910, issued, Mar.30, 1993 and Sep. 7, 1993, respectively both to Damani. Carrierssuitable for the preparation of compositions of the present inventionare well known in the art. Their selection will depend on secondaryconsiderations like taste, cost, and shelf stability, etc.

The compositions of the present invention may also be in the form ofnon-abrasive gels and subgingival gels, which may be aqueous ornon-aqueous. In still another aspect, the invention provides a dentalimplement impregnated with the present composition. The dental implementcomprises an implement for contact with teeth and other tissues in theoral cavity, said implement being impregnated with the presentcomposition. The dental implement can be impregnated fibers-includingdental floss or tape, chips, strips, films and polymer fibers.

In one embodiment, the compositions of the subject invention are in theform of dentifrices, such as toothpastes; tooth gels and tooth powders.Components of such toothpaste and tooth gels generally include one ormore of a dental abrasive (from about 6% to about 50%), a surfactant(from about 0.5% to about 10%), a thickening agent (from about 0.1% toabout 5%), a humectant (from about 10% to about 55%), a flavoring agent(from about 0.04% to about 2%), a sweetening agent (from about 0.1% toabout 3%), a coloring agent (from about 0.01% to about 0.5%) and water(from about 2% to about 45%). Such toothpaste or tooth gel may alsoinclude one or more of an anticaries agent (from about 0.05% to about0.3% as fluoride ion) and an anticalculus agent (from about 0.1% toabout 13%). Tooth powders, of course, contain substantially allnon-liquid components.

Other embodiments of the subject invention are liquid products,including mouthwashes or rinses, mouth sprays, dental solutions andirrigation fluids. Components of such mouthwashes and mouth spraystypically include one or more of water (from about 45% to about 95%),ethanol (from about 0% to about 25%), a humectant (from about 0% toabout 50%), a surfactant (from about 0.01% to about 7%), a flavoringagent (from about 0.04% to about 2%), a sweetening agent (from about0.1% to about 3%), and a coloring agent (from about 0.001% to about0.5%). Such mouthwashes and mouth sprays may also include one or more ofan anticaries agent (from about 0.05% to about 0.3% as fluoride ion) andan anticalculus agent (from about 0.1% to about 3%). Components ofdental solutions generally include one or more of water (from about 90%to about 99%), preservative (from about 0.01% to about 0.5%), thickeningagent (from 0% to about 5%), flavoring agent (from about 0.04% to about2%), sweetening agent (from about 0.1% to about 3%), and surfactant(from 0% to about 5%).

The present flavor system is particularly advantageous in masking theunpleasant aesthetics due to peroxide in such liquid products. In suchproducts, the peroxide is pre-solubilized and readily available tostimulate the nerves and taste receptors in the mouth when the productis introduced therein. During use of a semi-solid product such as atoothpaste, relatively lower levels of peroxide are available to producea sensory effect since the peroxide is slowly solubilized with salivaduring toothbrushing.

Types of orally acceptable carriers or excipients which may be includedin compositions of the present invention, along with specificnon-limiting examples, are discussed in the following paragraphs.

Tooth Substantive Agent

The present invention may include a tooth substantive agent such aspolymeric surface active agents (PMSA's), which are polyelectrolytes,more specifically anionic polymers. The PMSA's contain. anionic groups,e.g., phosphate, phosphonate, carboxy, or mixtures thereof, and thus,have the capability to interact with cationic or positively chargedentities. The “mineral” descriptor is intended to convey that thesurface activity or substantivity of the polymer is toward mineralsurfaces such as calcium phosphate minerals or teeth.

PMSA's are useful in the present compositions because of their stainprevention benefit. It is believed the PMSA's provide a stain preventionbenefit because of their reactivity or substantivity to mineralsurfaces, resulting in desorption of portions of undesirable adsorbedpellicle proteins, in particular those associated with binding colorbodies that stain teeth, calculus development and attraction ofundesirable microbial species. The retention of these PMSA's on teethcan also prevent stains from accruing due to disruption of binding sitesof color bodies on tooth surfaces.

The ability of PMSA's to bind stain promoting ingredients of oral careproducts such as stannous ions and cationic antimicrobials is alsobelieved to be helpful. The PMSA will also provide tooth surfaceconditioning effects which produce desirable effects on surfacethermodynamic properties and surface film properties, which impartimproved clean feel aesthetics both during and most importantly,following rinsing or brushing. Many of these polymeric agents are alsoknown or expected to provide tartar control benefits when applied inoral compositions, hence providing improvement in both the appearance ofteeth and their tactile impression to consumers.

The desired surface effects include: 1) creating a hydrophilic toothsurface immediately after treatment; and 2) maintaining surfaceconditioning effects and control of pellicle film for extended periodsfollowing product use, including post brushing or rinsing and throughoutmore extended periods. The effect of creating an increased hydrophilicsurface can be measured in terms of a relative decrease in water contactangles. The hydrophilic surface, importantly, is maintained on the toothsurface for an extended period after using the product.

The polymeric mineral surface active agents include any agent which willhave a strong affinity for the tooth surface, deposit a polymer layer orcoating on the tooth surface and produce the desired surfacemodification effects. Suitable examples of such polymers arepolyelectrolytes such as condensed phosphorylated polymers;polyphosphonates; copolymers of phosphate- or phosphonate-containingmonomers or polymers with other monomers such as ethylenicallyunsaturated monomers and amino acids or with other polymers such asproteins, polypeptides, polysaccharides, poly(acrylate),poly(acrylamide), poly(methacrylate), poly(ethacrylate),poly(hydroxyalkylmethacrylate), poly(vinyl alcohol), poly(maleicanhydride), poly(maleate) poly(amide), poly(ethylene amine),poly(ethylene glycol), poly(propylene glycol), poly(vinyl acetate) andpoly(vinyl benzyl chloride); polycarboxylates and carboxy-substitutedpolymers; and mixtures thereof. Suitable polymeric mineral surfaceactive agents include the carboxy-substituted alcohol polymers describedin U.S. Pat. Nos. 5,292,501; 5,213,789, 5,093,170; 5,009,882; and4,939,284; all to Degenhardt et al. and the diphosphonate-derivatizedpolymers in U.S. Pat. No. 5,011,913 to Benedict et al; the syntheticanionic polymers including polyacrylates and copolymers of maleicanhydride or acid and methyl vinyl ether (e.g., Gantrez), as described,for example, in U.S. Pat. No. 4,627,977, to Gaffar et al. A preferredpolymer is diphosphonate modified polyacrylic acid. Polymers withactivity must have sufficient surface binding propensity to desorbpellicle proteins and remain affixed to enamel surfaces. For toothsurfaces, polymers with end or side chain phosphate or phosphonatefunctions are preferred although other polymers with mineral bindingactivity may prove effective depending upon adsorption affinity.

Additional examples of suitable phosphonate containing polymeric mineralsurface active agents include the geminal diphosphonate polymersdisclosed as anticalculus agents in U.S. Pat. No. 4,877,603 toDegenhardt et al; phosphonate group containing copolymers disclosed inU.S. Pat. No. 4,749,758 to Dursch et al. and in GB 1,290,724 (bothassigned to Hoechst) suitable for use in detergent and cleaningcompositions; and the copolymers and cotelomers disclosed as useful forapplications including scale and corrosion inhibition, coatings, cementsand ion-exchange resins in U.S. Pat. No. 5,980,776 to Zakikhani et al.and U.S. Pat. No. 6,071,434 to Davis et al. Additional polymers includethe water-soluble copolymers of vinylphosphonic acid and acrylic acidand salts thereof disclosed in GB 1,290,724 wherein the copolymerscontain from about 10% to about 90% by weight vinylphosphonic acid andfrom about 90% to about 10% by weight acrylic acid, more particularlywherein the copolymers have a weight ratio of vinylphosphonic acid toacrylic acid of 70% vinylphosphonic acid to 30% acrylic acid; 50%vinylphosphonic acid to 50% acrylic acid; or 30% vinylphosphonic acid to70% acrylic acid. Other suitable polymers include the water solublepolymers disclosed by Zakikhani and Davis prepared by copolymerizingdiphosphonate or polyphosphonate monomers having one or more unsaturatedC═C bonds (e.g., vinylidene-1,1-diphosphonic acid and2-(hydroxyphosphinyl)ethylidene-1,1-diphosphonic acid), with at leastone further compound having unsaturated C═C bonds (e.g., acrylate andmethacrylate monomers), such as those having the following structure:

1. Co-Telomer of Acrylic Acid and2-(hydroxyphosphinyl)ethylidene-1,1-diphosphonic acid with Structure

2. Co-Polymer of Acrylic Acid and Vinyldiphosphonic Acid with Structure

Suitable polymers include the diphosphonate/acrylate polymers suppliedby Rhodia under the designation ITC 1087 (Average MW 3000-60,000) andPolymer 1154 (Average MW 6000-55,000).

A preferred PMSA will be stable with other components of the oral carecomposition such as ionic fluoride and metal ions. Also preferred arepolymers that have limited hydrolysis in high water contentformulations, thus permitting a simple single phase dentifrice ormouthrinse formulation. If the PMSA does not have these stabilityproperties, one option is a dual phase formulation with the polymericmineral surface active agent separated from the fluoride or otherincompatible component. Another option is to formulate non-aqueous,essentially non-aqueous or limited water compositions to minimizereaction between the PMSA and other components.

A preferred PMSA is a polyphosphate. A polyphosphate is generallyunderstood to consist of two or more phosphate molecules arrangedprimarily in a linear configuration, although some cyclic derivativesmay be present. Although pyrophosphates (n=2) are technicallypolyphosphates, the polyphosphates desired are those having around threeor more phosphate groups so that surface adsorption at effectiveconcentrations produces sufficient non-bound phosphate functions, whichenhance the anionic surface charge as well as hydrophilic character ofthe surfaces. The inorganic polyphosphate salts desired includetripolyphosphate, tetrapolyphosphate and hexametaphosphate, amongothers. Polyphosphates larger than tetrapolyphosphate usually occur asamorphous glassy materials. Preferred in this invention are the linearpolyphosphates having the formula:

XO(XPO₃)_(n)X

wherein X is sodium, potassium or ammonium and n averages from about 3to about 125. Preferred polyphosphates are those having n averaging fromabout 6 to about 21, such as those commercially known as Sodaphos (n≈6),Hexaphos (n≈13), and Glass H (n≈21) and manufactured by FMC Corporationand Astaris. These polyphosphates may be used alone or in combination.Polyphosphates are susceptible to hydrolysis in high water formulationsat acid pH, particularly below pH 5. Thus it is preferred to uselonger-chain polyphosphates, in particular Glass H with an average chainlength of about 21. It is believed such longer-chain polyphosphates whenundergoing hydrolysis produce shorter-chain polyphosphates which arestill effective to deposit onto teeth and provide a stain preventivebenefit.

Other polyphosphorylated compounds may be used in addition to or insteadof the polyphosphate, in particular polyphosphorylated inositolcompounds such as phytic acid, myo-inositol pentakis(dihydrogenphosphate); myo-inositol tetrakis(dihydrogen phosphate), myo-inositoltrikis(dihydrogen phosphate), and an alkali metal, alkaline earth metalor ammonium salt thereof. Preferred herein is phytic acid, also known asmyo-inositol 1,2,3,4,5,6-hexakis (dihydrogen phosphate) or inositolhexaphosphoric acid, and its alkali metal, alkaline earth metal orammonium salts. Herein, the term “phytate” includes phytic acid and itssalts as well as the other polyphosphorylated inositol compounds.

The amount of tooth substantive agent will typically be from about 0.1%to about 35% by weight of the total oral composition. In dentifriceformulations, the amount is preferably from about 2% to about 30%, morepreferably from about 5% to about 25%, and most preferably from about 6%to about 20%. In mouthrinse compositions, the amount of toothsubstantive agent is preferably from about 0.1% to 5% and morepreferably from about 0.5% to about 3%.

In addition to creating the surface modifying effects, the toothsubstantive agent may also function to solubilize insoluble salts. Forexample, Glass H has been found to solubilize insoluble stannous salts.Thus, in compositions containing stannous fluoride for example, Glass Hcontributes to decreasing the stain promoting effect of stannous.

Fluoride Source

It is common to have a water-soluble fluoride compound present indentifrices and other oral compositions in an amount sufficient to givea fluoride ion concentration in the composition, and/or when it is usedof from about 0.0025% to about 5.0% by weight, preferably from about0.005% to about 2.0% by weight, to provide anticaries effectiveness. Awide variety of fluoride ion-yielding materials can be employed assources of soluble fluoride in the present compositions. Examples ofsuitable fluoride ion-yielding materials are found in U.S. Pat. No.3,535,421, Oct. 20, 1970 to Briner et al. and U.S. Pat. No. 3,678,154,Jul. 18, 1972 to Widder et al. Representative fluoride ion sourcesinclude: stannous fluoride, sodium fluoride, potassium fluoride, sodiummonofluorophosphate, indium fluoride and many others. Stannous fluorideand sodium fluoride are preferred, as well as mixtures thereof.

Abrasives

Dental abrasives useful in the compositions of the subject inventioninclude many different materials. The material selected must be onewhich is compatible within the composition of interest and does notexcessively abrade dentin. Suitable abrasives include, for example,silicas including gels and precipitates, insoluble sodiumpolymetaphosphate, hydrated alumina, calcium carbonate, dicalciumorthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate,calcium polymetaphosphate, and resinous abrasive materials such asparticulate condensation products of urea and formaldehyde.

Another class of abrasives for use in the present compositions is theparticulate thermo-setting polymerized resins as described in U.S. Pat.No. 3,070,510 issued to Cooley & Grabenstetter on Dec. 25, 1962.Suitable resins include, for example, melamines, phenolics, ureas,melamine-ureas, melamine-formaldehydes, urea-formaldehyde,melamine-urea-formaldehydes, cross-linked epoxides, and cross-linkedpolyesters.

Silica dental abrasives of various types are preferred because of theirunique benefits of exceptional dental cleaning and polishing performancewithout unduly abrading tooth enamel or dentine. The silica abrasivepolishing materials herein, as well as other abrasives, generally havean average particle size ranging between about 0.1 to about 30 microns,and preferably from about 5 to about 15 microns. The abrasive can beprecipitated silica or silica gels such as the silica xerogels describedin Pader et al., U.S. Pat. No. 3,538,230, issued Mar. 2, 1970, andDiGiulio, U.S. Pat. No. 3,862,307, issued Jan. 21, 1975. Examplesinclude the silica xerogels marketed under the trade name “Syloid” bythe W.R. Grace & Company, Davison Chemical Division and precipitatedsilica materials such as those marketed by the J. M. Huber Corporationunder the trade name, Zeodent®, particularly the silicas carrying thedesignation Zeodent® 119, Zeodent® 118, Zeodent® 109 and Zeodent® 129.The types of silica dental abrasives useful in the toothpastes of thepresent invention are described in more detail in Wason, U.S. Pat. No.4,340,583, issued Jul. 29, 1982; and in commonly-assigned U.S. Pat. No.5,603,920, issued on Feb. 18, 1997; U.S. Pat. No. 5,589,160, issued Dec.31, 1996; U.S. Pat. No. 5,658,553, issued Aug. 19, 1997; U.S. Pat. No.5,651,958, issued Jul. 29, 1997, and U.S. Pat. No. 6,740,311, issued May25, 2004.

Mixtures of abrasives can be used such as mixtures of the various gradesof Zeodent® silica abrasives listed above. The total amount of abrasivein dentifrice compositions of the subject invention typically range fromabout 6% to about 70% by weight; toothpastes preferably contain fromabout 10% to about 50% of abrasives, by weight of the composition.Dental solution, mouth spray, mouthwash and non-abrasive gelcompositions of the subject invention typically contain little or noabrasive.

Anticalculus Agent

The present compositions may optionally include an additionalanticalculus agent, such as a pyrophosphate salt as a source ofpyrophosphate ion. The pyrophosphate salts useful in the presentcompositions include the dialkali metal pyrophosphate salts, tetraalkalimetal pyrophosphate salts, and mixtures thereof. Disodium dihydrogenpyrophosphate (Na₂H₂P₂O₇), tetrasodium pyrophosphate (Na₄P₂O₇), andtetrapotassium pyrophosphate (K₄P₂O₇) in their unhydrated as well ashydrated forms are the preferred species. In compositions of the presentinvention, the pyrophosphate salt may be present in one of three ways:predominately dissolved, predominately undissolved, or a mixture ofdissolved and undissolved pyrophosphate.

Compositions comprising predominately dissolved pyrophosphate refer tocompositions where at least one pyrophosphate ion source is in an amountsufficient to provide at least about 1.0% free pyrophosphate ions. Theamount of free pyrophosphate ions may be from about 1% to about 15%,from about 1.5% to about 10% in one embodiment, and from about 2% toabout 6% in another embodiment. Free pyrophosphate ions may be presentin a variety of protonated states depending on the pH of thecomposition.

Compositions comprising predominately undissolved pyrophosphate refer tocompositions containing no more than about 20% of the totalpyrophosphate salt dissolved in the composition, preferably less thanabout 10% of the total pyrophosphate dissolved in the composition.Tetrasodium pyrophosphate salt is a preferred pyrophosphate salt inthese compositions. Tetrasodium pyrophosphate may be the anhydrous saltform or the decahydrate form, or any other species stable in solid formin the dentifrice compositions. The salt is in its solid particle form,which may be its crystalline and/or amorphous state, with the particlesize of the salt preferably being small enough to be aestheticallyacceptable and readily soluble during use. The amount of pyrophosphatesalt useful in making these compositions is any tartar control effectiveamount, generally from about 1.5% to about 15%, preferably from about 2%to about 10%, and most preferably from about 3% to about 8%, by weightof the dentifrice composition.

Compositions may also comprise a mixture of dissolved and undissolvedpyrophosphate salts. Any of the above mentioned pyrophosphate salts maybe used.

The pyrophosphate salts are described in more detail in Kirk-OthmerEncyclopedia of Chemical Technology, Third Edition, Volume 17,Wiley-Interscience Publishers (1982).

Optional agents to be used in place of or in combination with thepyrophosphate salt include such known materials as synthetic anionicpolymers, including polyacrylates and copolymers of maleic anhydride oracid and methyl vinyl ether (e.g., Gantrez), as described, for example,in U.S. Pat. No. 4,627,977, to Gaffar et al., as well as, e.g.,polyamino propane sulfonic acid (AMPS), diphosphonates (e.g., EHDP;AHP), polypeptides (such as polyaspartic and polyglutamic acids), andmixtures thereof.

Chelating Agents

Another optional agent is a chelating agent, also called sequestrants,such as gluconic acid, tartaric acid, citric acid andpharmaceutically-acceptable salts thereof. Chelating agents are able tocomplex calcium found in the cell walls of the bacteria. Chelatingagents can also disrupt plaque by removing calcium from the calciumbridges which help hold this biomass intact. However, it is not desiredto use a chelating agent which has an affinity for calcium that is toohigh, as this may result in tooth demineralization, which is contrary tothe objects and intentions of the present invention. Suitable chelatingagents will generally have a calcium binding constant of about 10¹ to10⁵ to provide improved cleaning with reduced plaque and calculusformation. Chelating agents also have the ability to complex withmetallic ions and thus aid in preventing their adverse effects on thestability or appearance of products. Chelation of ions, such as iron orcopper, helps retard oxidative deterioration of finished products.

Examples of suitable chelating agents are sodium or potassium gluconateand citrate; citric acid/alkali metal citrate combination; disodiumtartrate; dipotassium tartrate; sodium potassium tartrate; sodiumhydrogen tartrate; potassium hydrogen tartrate; sodium, potassium orammonium polyphosphates and mixtures thereof. The amounts of chelatingagent suitable for use in the present invention are about 0.1% to about2.5%, preferably from about 0.5% to about 2.5% and more preferably fromabout 1.0% to about 2.5%.

Still other chelating agents suitable for use in the present inventionare the anionic polymeric polycarboxylates. Such materials are wellknown in the art, being employed in the form of their free acids orpartially or preferably fully neutralized water soluble alkali metal(e.g. potassium and preferably sodium) or ammonium salts. Examples are1:4 to 4:1 copolymers of maleic anhydride or acid with anotherpolymerizable ethylenically unsaturated monomer, preferably methyl vinylether (methoxyethylene) having a molecular weight (M.W.) of about 30,000to about 1,000,000. These copolymers are available for example asGantrez AN 139 (M.W. 500,000), AN 119 (M.W. 250,000) and S-97Pharmaceutical Grade (M.W. 70,000), of GAF Chemicals Corporation.

Other operative polymeric polycarboxylates include the 1:1 copolymers ofmaleic anhydride with ethyl acrylate, hydroxyethyl methacrylate,N-vinyl-2-pyrrolidone, or ethylene, the latter being available forexample as Monsanto EMA No. 1103, M.W. 10,000 and EMA Grade 61, and 1:1copolymers of acrylic acid with methyl or hydroxyethyl methacrylate,methyl or ethyl acrylate, isobutyl vinyl ether or N-vinyl-2-pyrrolidone.

Additional operative polymeric polycarboxylates are disclosed in U.S.Pat. No. 4,138,477, Feb. 6, 1979 to Gaffar and U.S. Pat. No. 4,183,914,Jan. 15, 1980 to Gaffar et al. and include copolymers of maleicanhydride with styrene, isobutylene or ethyl vinyl ether; polyacrylic,polyitaconic and polymaleic acids; and sulfoacrylic oligomers of M.W. aslow as 1,000 available as Uniroyal ND-2.

Other Active Agents

The present invention may optionally include other agents, such asantimicrobial agents. Included among such agents are water insolublenon-cationic antimicrobial agents such as halogenated diphenyl ethers,phenolic compounds including phenol and its homologs, mono andpoly-alkyl and aromatic halophenols, resorcinol and its derivatives,bisphenolic compounds and halogenated salicylanilides, benzoic esters,and halogenated carbanilides. The water soluble antimicrobials includequaternary ammonium salts and bis-biquanide salts, and triclosanmonophosphate. The quaternary ammonium agents include those in which oneor two of the substitutes on the quaternary nitrogen has a carbon chainlength (typically alkyl group) from about 8 to about 20, typically fromabout 10 to about 18 carbon atoms while the remaining substitutes(typically alkyl or benzyl group) have a lower number of carbon atoms,such as from about 1 to about 7 carbon atoms, typically methyl or ethylgroups. Dodecyl trimethyl ammonium bromide, tetradecylpyridiniumchloride, domiphen bromide, N-tetradecyl-4-ethyl pyridinium chloride,dodecyl dimethyl(2-phenoxyethyl)ammonium bromide, benzyl dimethylstearylammonium chloride, cetyl pyridinium chloride, quaternized5-amino-1,3-bis(2-ethyl-hexyl)-5-methyl hexa hydropyrimidine,benzalkonium chloride, benzethonium chloride and methyl benzethoniumchloride are exemplary of typical quaternary ammonium antibacterialagents. Other compounds are bis[4-(R-amino)-1-pyridinium]alkanes asdisclosed in U.S. Pat. No. 4,206,215, issued Jun. 3, 1980, to Bailey.Other antimicrobials such as copper salts, zinc salts and stannous saltsmay also be included. Also useful are enzymes, includingendoglycosidase, papain, dextranase, mutanase, and mixtures thereof.Such agents are disclosed in U.S. Pat. No. 2,946,725, Jul. 26, 1960, toNorris et al. and in U.S. Pat. No. 4,051,234, Sep. 27, 1977 to Gieske etal. Preferred antimicrobial agents include zinc salts, stannous salts,cetyl pyridinium chloride, chlorhexidine, triclosan, triclosanmonophosphate, and flavor oils such as thymol. Triclosan and otheragents of this type are disclosed in Parran, Jr. et al., U.S. Pat. No.5,015,466, issued May 14, 1991, and U.S. Pat. No. 4,894,220, Jan. 16,1990 to Nabi et al. These agents provide anti-plaque benefits and aretypically present at levels of from about 0.01% to about 5.0%, by weightof the composition.

Another optional active agent that may be added to the present.compositions is a dentinal desensitizing agent to controlhypersensitivity, such as salts of potassium, calcium, strontium and tinincluding nitrate, chloride, fluoride, phosphates, pyrophosphate,polyphosphate, citrate, oxalate and sulfate.

Surfactants

The present compositions may also comprise surfactants, also commonlyreferred to as sudsing agents. Suitable surfactants are those which arereasonably stable and foam throughout a wide pH range. The surfactantmay be anionic, nonionic, amphoteric, zwitterionic, cationic, ormixtures thereof.

Anionic surfactants useful herein include the water-soluble salts ofalkyl sulfates having from 8 to 20 carbon atoms in the alkyl radical(e.g., sodium alkyl sulfate) and the water-soluble salts of sulfonatedmonoglycerides of fatty acids having from 8 to 20 carbon atoms. Sodiumlauryl sulfate (SLS) and sodium coconut monoglyceride sulfonates areexamples of anionic surfactants of this type. Other suitable anionicsurfactants are sarcosinates, such as sodium lauroyl sarcosinate,taurates, sodium lauryl sulfoacetate, sodium lauroyl isethionate, sodiumlaureth carboxylate, and sodium dodecyl benzenesulfonate. Mixtures ofanionic surfactants can also be employed. Many suitable anionicsurfactants are disclosed by Agricola et al., U.S. Pat. No. 3,959,458,issued May 25, 1976. The present composition typically comprises ananionic surfactant at a level of from about 0.025% to about 9%, fromabout 0.05% to about 5% in some embodiments, and from about 0.1% toabout 1% in other embodiments.

Another suitable surfactant is one selected from the group consisting ofsarcosinate surfactants, isethionate surfactants and tauratesurfactants. Preferred for use herein are alkali metal or ammonium saltsof these surfactants such as the sodium and potassium salts of thefollowing: lauroyl sarcosinate, myristoyl sarcosinate, palmitoylsarcosinate, stearoyl sarcosinate and oleoyl sarcosinate. Thesarcosinate surfactant may be present in the compositions of the presentinvention from about 0.1% to about 2.5%, preferably from about 0.5% toabout 2.0% by weight of the total composition.

Cationic surfactants useful in the present invention include derivativesof aliphatic quaternary ammonium compounds having one long alkyl chaincontaining from about 8 to 18 carbon atoms such as lauryltrimethylammonium chloride; cetyl pyridinium chloride; cetyltrimethylammonium bromide;di-isobutylphenoxyethyl-dimethylbenzylammonium chloride; coconutalkyltrimethylammonium nitrite; cetyl pyridinium fluoride; etc.Preferred compounds are the quaternary ammonium fluorides described inU.S. Pat. No. 3,535,421, Oct. 20, 1970, to Briner et al., where saidquaternary ammonium fluorides have detergent properties. Certaincationic surfactants can also act as germicides in the compositionsdisclosed herein. Cationic surfactants such as chlorhexidine, althoughsuitable for use in the current invention, are not preferred due totheir capacity to stain the oral cavity's hard tissues. Persons skilledin the art are aware of this possibility and should incorporate cationicsurfactants with this limitation in mind.

Nonionic surfactants that can be used in the compositions of the presentinvention include compounds produced by the condensation of alkyleneoxide groups (hydrophilic in nature) with an organic hydrophobiccompound which may be aliphatic or alkylaromatic in nature. Examples ofsuitable nonionic surfactants include the Pluronics, polyethylene oxidecondensates of alkyl phenols, products derived from the condensation ofethylene oxide with the reaction product of propylene oxide and ethylenediamine, ethylene oxide condensates of aliphatic alcohols, long chaintertiary amine oxides, long chain tertiary phosphine oxides, long chaindialkyl sulfoxides and mixtures of such materials.

Zwitterionic synthetic surfactants useful in the present inventioninclude derivatives of aliphatic quaternary ammonium, phosphonium, andsulfonium compounds, in which the aliphatic radicals can be straightchain or branched, and wherein one of the aliphatic substituentscontains from about 8 to 18 carbon atoms and one contains an anionicwater-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphateor phosphonate.

Suitable betaine surfactants are disclosed in U.S. Pat. No. 5,180,577 toPolefka et al., issued Jan. 19, 1993. Typical alkyl dimethyl betainesinclude decyl betaine or 2-(N-decyl-N,N-dimethylammonio)acetate, cocobetaine or 2-(N-coc-N,N-dimethyl ammonio)acetate, myristyl betaine,palmityl betaine, lauryl betaine, cetyl betaine, cetyl betaine, stearylbetaine, etc. The amidobetaines are exemplified by cocoamidoethylbetaine, cocoamidopropyl betaine, lauramidopropyl betaine and the like.The betaines of choice include cocoamidopropyl betaines and preferably,the lauramidopropyl betaine.

Thickening Agents

In preparing toothpaste or gels, thickening agents are added to providea desirable consistency to the composition, to provide desirable activerelease characteristics upon use, to provide shelf stability, and toprovide stability of the composition, etc. Suitable thickening agentsinclude one or a combination of carboxyvinyl polymers, carrageenan,hydroxyethyl cellulose (HEC), natural and synthetic clays (e.g., Veegumand laponite) and water soluble salts of cellulose ethers such as sodiumcarboxymethylcellulose (CMC) and sodium carboxymethyl hydroxyethylcellulose. Natural gums such as gum karaya, xanthan gum, gum arabic, andgum tragacanth can also be used. Colloidal magnesium aluminum silicateor finely divided silica can be used as part of the thickening agent tofurther improve texture.

Suitable carboxyvinyl polymers useful as thickening or gelling agentsinclude carbomers which are homopolymers of acrylic acid crosslinkedwith an alkyl ether of pentaerythritol or an alkyl ether of sucrose.Carbomers are commercially available from B.F. Goodrich as the Carbopol®series, including Carbopol 934, 940, 941, 956, and mixtures thereof.

Thickening agents are typically present in an amount from about 0.1% toabout 15%, preferably from about 2% to about 10%, more preferably fromabout 4% to about 8%, by weight of the total toothpaste or gelcomposition, can be used. Higher concentrations may be used for chewinggums, lozenges and breath mints, sachets, non-abrasive gels andsubgingival gels.

Humectants

Another optional carrier material of the present compositions is ahumectant. The humectant serves to keep toothpaste compositions fromhardening upon exposure to air, to give compositions a moist feel to themouth, and, for particular humectants, to impart desirable sweetness offlavor to toothpaste compositions. The humectant, on a pure humectantbasis, generally comprises from about 0% to about 70%, preferably fromabout 5% to about 25%, by weight of the compositions herein. Suitablehumectants for use in compositions of the subject invention includeedible polyhydric alcohols such as glycerin, sorbitol, xylitol, butyleneglycol, polyethylene glycol, propylene glycol and trimethyl glycine.

Miscellaneous Carrier Materials

Water employed in the preparation of commercially suitable oralcompositions should preferably be of low ion content and free of organicimpurities. Water may comprise up to about 99% by weight of the aqueouscompositions herein. These amounts of water include the free water whichis added plus that which is introduced with other materials, such aswith sorbitol.

The present invention may also include an alkali metal bicarbonate salt,which may serve a number of functions including abrasive, deodorant,buffering and adjusting pH. Alkali metal bicarbonate salts are solublein water and unless stabilized, tend to release carbon dioxide in anaqueous system. Sodium bicarbonate, also known as baking soda, is acommonly used alkali metal bicarbonate salt. The present composition maycontain from about 0.5% to about 30%, preferably from about 0.5% toabout 15%, and most preferably from about 0.5% to about 5% of an alkalimetal bicarbonate salt.

The pH of the present compositions may be adjusted through the use ofbuffering agents. Buffering agents, as used herein, refer to agents thatcan be used to adjust the pH of aqueous compositions such as mouthrinsesand dental solutions preferably to a range of about pH 4.0 to about pH6.0 for peroxide stability. Buffering agents include sodium bicarbonate,monosodium phosphate, trisodium phosphate, sodium hydroxide, sodiumcarbonate, sodium acid pyrophosphate, citric acid, and sodium citrate.Buffering agents are typically included at a level of from about 0.5% toabout 10%, by weight of the present compositions.

Poloxamers may be employed in the present. compositions. A poloxamer isclassified as a nonionic surfactant and may also function as anemulsifying agent, binder, stabilizer, and other related functions.Poloxamers are difunctional block-polymers terminating in primaryhydroxyl groups with molecular weights ranging from 1,000 to above15,000. Poloxamers are sold under the tradename of Pluronics andPluraflo by BASF. Suitable poloxamers for this invention are Poloxamer407 and Pluraflo MA370.

Other emulsifying agents that may be used in the present compositionsinclude polymeric emulsifiers such as the Pemulen® series available fromB.F. Goodrich, and which are predominantly high molecular weightpolyacrylic acid polymers useful as emulsifiers for hydrophobicsubstances.

Titanium dioxide may also be added to the present composition. Titaniumdioxide is a white powder which adds opacity to the compositions.Titanium dioxide generally comprises from about 0.25% to about 5% byweight of dentifrice compositions.

Other optional agents that may be used in the present compositionsinclude dimethicone copolyols selected from alkyl- andalkoxy-dimethicone copolyols, such as C12 to C20 alkyl dimethiconecopolyols and mixtures thereof. Highly preferred is cetyl dimethiconecopolyol marketed under the trade name Abil EM90. The dimethiconecopolyol is generally present in a level of from about 0.01% to about25%, preferably from about 0.1% to about 5%, more preferably from about0.5% to about 1.5% by weight. The dimethicone copolyols aid in providingpositive tooth feel benefits.

Method of Use

The present invention also relates to methods for whitening teeth andpreventing staining. The benefits of these compositions may increaseover time when the composition is used repeatedly.

The method of treatment herein comprises contacting a subject's dentalenamel surfaces and mucosa in the mouth with the oral compositionsaccording to the present invention. The method of treatment may be bybrushing with a dentifrice or rinsing with a dentifrice slurry ormouthrinse. Other methods include contacting the topical oral gel,dentures product, mouthspray, or other form with the subject's teeth andoral mucosa. The subject may be any person or animal whose tooth surfacecontact the oral composition. By animal is meant to include householdpets or other domestic animals, or animals kept in captivity.

For example, a method of treatment may include a person brushing a dog'steeth with one of the dentifrice compositions. Another example wouldinclude the rinsing of a cat's mouth with an oral composition for asufficient amount of time to see a benefit. Pet care products such aschews and toys may be formulated to contain the present oralcompositions. The composition is incorporated into a relatively supplebut strong and durable material such as rawhide, ropes made from naturalor synthetic fibers, and polymeric articles made from nylon, polyesteror thermoplastic polyurethane. As the animal chews, licks or gnaws theproduct, the incorporated active elements are released into the animal'soral cavity into a salivary medium, comparable to an effective brushingor rinsing.

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. These examples are givensolely for the purpose of illustration and are not to be construed aslimitations of the present invention as many variations thereof arepossible without departing from the spirit and scope.

Example I Mouthrinse Compositions

Mouthrinse compositions according to the present invention (IA-IF) areshown below with amounts of components in weight %. These compositionsare made using conventional methods. The mouthrinse compositions werejudged in consumer testing as having a pleasant high-impact minty tasteduring use and providing noticeable fresh breath.

Ingredient Ex. IA Ex. IB Ex. IC Ex. ID Ex. IE Ex. IF 35% H₂O₂ 4.2864.286 4.286 2.143 4.286 4.286 solution Menthol 0.075 0.020 0.040 0.0400.030 0.040 WS-3 Coolant 0.020 0.030 0.020 0.020 0.015 0.025 WS-23Coolant 0.020 0.010 0.015 0.010 Artificial Mint 0.145 0.135 0.135 0.1500.135 0.135 Flavor¹ Poloxamer 407 0.750 0.750 0.750 0.100 0.100 0.100Glycerin 11.000 11.000 11.000 20.000 20.000 20.000 Propylene 3.000 3.0004.000 4.000 4.000 Glycol Sucralose 0.050 — — Sodium 0.080 — 0.068 0.0600.080 0.060 Saccharin Polyphosphate² 2.0 1.000 Cetyl 0.074 0.100 0.100Pyridinium Chloride Na Citrate 0.212 0.212 Citric Acid 0.052 0.052 0.052Alcohol, USP 5.000 Water, QS QS QS QS QS QS Purified, USP ¹ArtificialMint Flavor comprises methyl salicylate, cinnnamic alcohol, eucalyptol,menthone and other flavor agents. A mint flavor comprising natural oils(peppermint, anise, clove bud oil, sweet birch) may be used instead ofthe artificial mint flavor. ²Polyphosphate is Glass H (n ≈ 21) suppliedby Astaris.

Example II Dual-Phase Dentifrice Compositions

Dual phase dentifrice compositions according to the present inventionare comprised of a first dentifrice composition (IIA-IIC) containingperoxide and a second dentifrice composition (IID-IIE), dispensedpreferably at a 50:50 ratio. These compositions are made usingconventional methods.

First Dentifrice Second Dentifrice Ingredient IIA IIB IIC IID IIE IIFGlass H Polyphosphate 7.00 7.00 Sodaphos Polyphosphate 7.00 CalciumPeroxide 1.00 0.40 5.00 Sodium Fluoride 0.486 0.486 Stannous Fluoride0.908 Stannous Chloride 3.000 Sodium Gluconate 4.160Carboxymethycellulose 0.60 0.60 0.60 Carbomer 0.20 Artificial MintFlavor¹ 1.00 1.00 1.00 0.40 0.90 1.00 Menthol 0.075 0.020 0.040 WS-3Coolant 0.020 0.030 0.020 WS-23 Coolant 0.020 0.010 0.30 0.40 0.40 Color0.30 0.40 0.30 Glycerin 43.20 26.80 24.20 44.514 9.00 28.992 Sorbitol29.594 Poloxamer 407 5.00 5.00 5.00 21.00 15.500 Polyethylene Glycol3.00 3.00 3.00 3.00 Propylene Glycol 5.00 5.00 5.00 Sodium AlkylSulfate⁽²⁾ 4.00 4.00 4.00 4.00 Silica 20.00 22.00 22.00 22.50 23.000Sodium Hydroxide⁽³⁾ 1.000 Sodium Bicarbonate 15.00 15.00 SodiumCarbonate 2.00 2.00 2.00 Sodium Saccharin 0.50 0.50 0.50 0.30 0.50 0.30Titanium Dioxide 0.50 0.50 0.50 Xanthan Gum 0.20 0.20 0.20 0.60 SodiumAcid Pyrophosphate 0.50 Tetrasodium Pyrophosphate 3.22 Water QS QS QS QSQS QS ¹Artificial Mint Flavor comprises methyl salicylate, cinnnamicalcohol, eucalyptol, menthone and other flavor agents. A mint flavorcomprising natural oils (peppermint, anise, clove bud oil, sweet birch)may be used instead of the artificial mint flavor. ⁽²⁾27.9% solution⁽³⁾50% solution

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. An oral care composition (a) from about 0.01% to about 30% by weightof the composition of a peroxide source, (b) a flavor compositioncomprising a coolant combination of menthol and at least one secondarycoolant and one or a mixture of flavor components that maintain aconsistent flavor profile in the presence of peroxide, and (c) anorally-acceptable carrier, wherein the flavor composition effectivelymasks undesirable aesthetics derived from peroxide and provides a highimpact refreshing taste and sensation.
 2. An oral care compositionaccording to claim 1 wherein the peroxide source is selected from thegroup consisting peroxides, perborates, percarbonates, peroxyacids,persulfates, and mixtures thereof.
 3. An oral care composition accordingto claim 1 wherein the peroxide source is selected from the groupconsisting of hydrogen peroxide, urea peroxide, calcium peroxide, sodiumpercarbonate, and mixtures thereof.
 4. An oral care compositionaccording to claim 1 comprising a total amount of menthol and secondarycoolant of from about 0.03% to about 1.5% by weight of the composition,wherein menthol comprises at least about 0.015% by weight of thecomposition.
 5. An oral care composition according to claim 1 whereinthe secondary coolant is selected from carboxamides, ketals, diols,menthyl esters and mixtures thereof.
 6. An aqueous oral care compositionaccording to claim 1, further comprising an antimicrobial activeselected from cetyl pyridinium chloride, domiphen bromide, zinc salts,stannous salts, chlorhexidine, triclosan, triclosan monophosphate andmixtures thereof.
 7. An oral care composition according to claim 1 inthe form of a dentifrice or mouthrinse.
 8. An oral care composition (a)from about 0.01% to about 10% by weight of the composition of a peroxidesource selected from hydrogen peroxide or urea peroxide, (b) from about0.03% to about 0.6% by weight of the composition of a coolantcombination of menthol and at least one secondary coolant, whereinmenthol comprises at least about 0.015% by weight of the composition (c)one or a mixture of flavor components selected from methyl salicylate,ethyl salicylate, methyl cinnamate, ethyl cinnamate, butyl cinnamate,ethyl butyrate, ethyl acetate, methyl anthranilate, iso-amyl acetate,iso-amyl butyrate, allyl caproate, eugenol, eucalyptol, thymol, cinnamicalcohol, cinnamic aldehyde, octanol, octanal, decanol, decanal,phenylethyl alcohol, benzyl alcohol, benzaldehyde, alpha-terpineol,linalool, limonene, citral, vanillin, ethyl vanillin, propenyl guaethol,maltol, ethyl maltol, heliotropin, anethole, dihydroanethole, carvone,oxanone, menthone, p-damascenone, ionone, gamma decalactone, gammanonalactone, gamma undecalactone, and4-hydroxy-2,5-dimethyl-3(2H)-furanone, and (d) an orally-acceptableaqueous carrier, wherein undesirable aesthetics derived from peroxideare effectively masked and the composition provides a consistent flavorprofile and a high impact refreshing taste and sensation.
 9. An aqueousoral care composition according to claim 8 wherein the secondary coolantis selected from carboxamides, ketals, diols, menthyl esters andmixtures thereof.
 10. An aqueous oral care composition according toclaim 8, further comprising an antimicrobial active selected from cetylpyridinium chloride, domiphen bromide, zinc salts, stannous salts,chlorhexidine, triclosan, triclosan monophosphate and mixtures thereof.